Reaction products of an amine and a methyl vinyl ether-maleic anhydride copolymer

ABSTRACT

LIQUID HYDROCARBON COMPOSITIONS ARE PROVIDED CONTAINING, IN AN AMOUNT SUFFICIENT TO IMPART ANTI-STATIC PROPERTIES, THE REACTION PRODUCT OF AN AMINE AND A METHYL VINYL ETHER-MALEIC ANHYDRIDE COPOLYMER.

United States Patent Int. Cl. C08g 20/20 US. Cl. 26078 UA 1 Qlaim ABSTRACT OF THE DISCLOSURE Liquid hydrocarbon compositions are provided containing, in an amount suflicient to impart anti-static properties, the reaction product of an amine and a methyl vinyl ether-maleic anhydride copolymer.

CROSS REFERENCE TO RELATED APPLICATIONS This application is a division of our copending application Ser. No. 747,808, filed July 26, 1968, now US. Pat. 3,578,421, issued May 11, 1971.

BACKGROUND OF THE INVENTION (1) Field of the invention This invention relates to organic liquids having desirable anti-static properties, and, in one of its aspects, relates more particularly to organic liquid compositions in the form of volatile organic liquids such as hydrocarbon fuels or solvents which possess low electrical conductivity which, when they accumulate electrostatic charges, may give rise to the hazards of ignition or explosion. Still more particularly in this aspect, the invention relates to the improvement of such organic liquids by incorporating therein, additives which are effective in increasing the electrical conductivity of such liquids to the extent that accumulation of electrostatic charges, with attendant danger of ignition or explosion, is significantly minimized, particularly in the handling, transportation or treatment of such liquids.

(2) Description of the prior art Prior to the present invention, the low electrical conductivity of many volatile organic liquid compositions has presented the problem of controlling static buildup, particularly during handling and transportation, for the purpose of insuring safe and effective distribution without the concomitant danger of ignition or explosion. For example, volatile organic liquids such as hydrocarbon fuels (e.g. gasoline, jet fuels, turbine fuels and the like), or light hydrocarbon oils employed for such purposes as solvents or cleaning fluids for textiles, possess a very low degree of electrical conductivity. In the use of such fluids, electrostatic charges, which may be generated by handling, operation or other means, tend to form on the surface, and may result in sparks, thus resulting in ignition or explosion. These hazards may be encountered merely in the handling or transportation of such organic liquids and even in operations, such as centrifuging, in which a solid is separated from a volatile liquid, during which electrostatic charges can accumulate.

Various materials have heretofore been proposed for incorporation into such organic liquid compositions for increasing their electrical conductivity and thus reduce the aforementioned dangers of ignition and explosion. Such materials, however, have not been proved to be sufliciently effective in increasing the desired electrical "ice conductivity of these fluids and, in many instances, have been found to be too costly for the relatively small degree of increased protection which they are capable of providing.

SUMMARY OF THE INVENTION In accordance with the present invention, improved liquid hydrocarbon compositions are providid containing, in an amount sufficient to impart anti-static properties, the reaction product of an amine and a methyl vinyl ether-maleic anhydride copolymer. The incorporation of these anti-static agents in the liquid composition, imparts increased electrical conductivity to an extent greater than that which has heretofore been realized with many other anti-static materials.

In general, the present invention, in its preferred applications, contemplates organic liquid compositions which normally are capable of accumulating a relatively large degree of electrostatic charge resulting in the aforementioned hazards of ignition and explosion, h'aving incorporated therein a small amount of the aforementioned reaction product, usually from about 0.1 to about 200, and preferably from about 1 to about 10 pounds, per thousand barrels of the total volume of the liquid composition.

A field of specific applicability of the present invention is in the improvement of organic liquid compositions in the form of pertoleum distillate fuel oils having an initial boiling point from about F. to about F. and an end boiling point from about 250 F. to about 1000 F. It should be noted, in this respect, that the term distillate fuel oils" is not intended to be restricted to straight-run distillate fractions. These distillate fuel oils can be straight-run distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils, or mixtures of straight-run distillate fuel oils, naphthas and the like, with cracked distillate stocks. Moreover, such fuel oils can be treated in accordance with well-known commercial methods, such as acid or caustic treatment, hydrogenation, solvent refining, clay treatment, and the like.

The distillate fuel oils are characterized by their relatively low viscosity, pour point and the like. The principal property which characterizes these contemplated hydrocarbons, however, is their distillation range. As hereinbefore indicated, this range will lie between about 75 F. and about 1000 F. Obviously, the distillation range of each individual fuel oil will cover a narrower boiling range, falling nevertheless, within the above-specified limits. Likewise, each fuel oil will boil substantially, continuously, throughout its distillation range.

Particularly contemplated among the fuel oils are Nos. 1, 2 and 3 fuel oils, used in heating and as Diesel fuel oils, gasoline, turbine fuels and the jet combustion fuels, as previously indicated. The domestic fuel oils generally conform to the specifications set forth in ASTM Specification D396-48T. Specifications for Diesel fuels are denfied in ASTM Specification D975-48T. Typical jet fuels are defined in Military Specification MIL-F-5624B.

The novel anti-static agents of the present invention may comprise the reaction product of any amine and the aforementioned methyl vinyl ether-maleic anhydride copolymer. Particularly preferred, and representative of such amines are: primary amines having a tertiary carbon atom attached to an amino group and containing from about 12 to about 15 carbon atoms per amine molecule (often referred to in the literature as Primene 81R) or primary amines having a tertiary carbon atom attached to an amino group and containing from about 18 to about 24 carbon atoms per amine molecule (often referred to in the literature as Primene J MT); fatty amines, as exemplified' by primary oleylamine, di-secondary cocoamine and tri-caprylyl amine; alkylaryl amines, as exemplified by phenylstearylamine; and complexed fatty acid fatty d1- amines, as exemplified by the condensation reaction product of 1 mol of oleyldiamine and 1 mol of a tall oil fatty acid. It will be understood, of course, that the reaction products of other amines and the aforementioned methyl vinyl ether-maleic anhydride copolymer may also be successfully incorporated into organic liquid compositions for their beneficial anti-static effect.

The aforementioned methyl Winyl ether-maleic anhydried copolymer is a commercially available material in which copolymerization between the methyl vinyl ether and the maleic anhydride is conducted in a mol ratio of from 1:1. This copolymer is described in the literature as having the following structure:

wherein n is an integer greater than 1. D

The literature further describes the following physical properties for the aforementioned copolymer. Appearance White, flufiy powder. Softening point range C.) 200-225.

Specific gravity of film 1.37.

Bulk density of powder (lb./ cu. ft). 20.

Angle of respose (degrees) 39.

Residual free maleic anhydride Nil. pH 5% aqueous solution (free Approx. 2.

acid).

Unit molecular weight 156.

(anhydride).

Unit molecular weight (free 174.

(acid).

Insofar as the reaction between the amine and the copolymer are concerned, it is found that the reaction product can be produced by employing the amine and the copolymer in a mol ratio of from about 1:1 to about 2:1, as more fully hereinafter described.

DESCRIPTION OF SPECIFIC EMBODIMENTS The following examples will serve to illustrate the preparation of the novel anti-static agents of the present invention, and the affect thereof when these agents are present in organic liquid compositions for the purpose of effectively imparting anti-static properties thereto, and particularly with respect to liquid hydrocarbon fuels.

Example 1 A mixture of 85 grams (0.4 mol) of Primene 81R 31.2 grams (0.2 mol) of the aforementioned methyl vinyl ethermaleic anhydride copolymer of low molecular weight, and 232 grams of xylene, as a diluent, was stirred at 140 C. for a period of three hours and resulted in a xylene solution of the aforementioned amine mixture-copolymer reaction product.

Example 2 A mixture of 125 grams (0.4 mol) of Primene JMT, 2 31.2 grams (0.2 mol) of the aforementioned methyl vinyl ethermaleic anhydride copolymer, of the same molecular weight, as employed in Example 1, and 312 grams of xylene, as a diluent, was stirred at 140 C. for a period of about three hours and resulted in a xylene solution of the aforementioned amine mixture-copolymer reaction product.

A mixture of primary amines having a tertiary carbon atom attached to the amino (NH2) group, containing from about 12 to about 15 carbon atoms per amine molecule.

A mixture of primary amines having a tertiary carbon atom attached to the amino (NH2) group containing from about 18 to about 24 carbon atoms per amine molecule.

Example 3 A mixture of 125 grams (0.4 mol) of Primene JMT, 31.2 grams (0.2 mol) of the aforementioned methyl vinyl ethermaleic anhydride copolymer of medium molecular weight, and 312 grams of xylene, as a diluent, was stirred at 140 C. for a period of about 3 hours and resulted in a xylene solution of the aforementioned amine mixturecopolymer reaction product.

Example 4 A mixture of 125 grams (0.4 mol) of Primene JMT, 31.2 grams (0.2 mol) of the aforementioned methyl vinyl ethermaleic anhydride copolymer of high molecular weight, and 312 grams of xylene, as a diluent, was stirred at 140 C. for a period of about three hours and resulted in a xylene solution of the aforementioned amine mixturecopolymer reaction product.

Example 5 A mixture of 123 grams (0.4 mol) of primary oleylamine, 31.2 grams (0.2 mol) of the aforementioned copolymer of Example 1 and 308 grams of xylene, as a diluent, was stirred at C. for a period of about three hours and resulted in a xylene solution of the reaction product of the aforementioned primary oleylamine and the methyl vinyl ether-maleic anhydride copolymer.

Example 6 A mixture of 140 grams (0.4 mol) of phenylstearylamine, 31.2 grams (0.2 mol) of the aforementioned copolymer of Example 1 and 342 grams of xylene, as a diluent, was stirred at a temperature of from about 115 C. to about C. for a period of about three hours and resulted in a xylene solution of the reaction product of the aforementioned phenylstearylamine and the methyl vinyl ether-maleic anhydride copolymer.

Example 7 A mixture of 160 grams (0.4 mol) of di-secondary cocoamine, 31.2 grams (0.2 mol) of the aforementioned copolymer of Example 1 and 382 grams of xylene, as a diluent, was stirred at C. for a period of about two hours and resulted in a xylene solution of the reaction product of the aforementioned di-secondary cocoamine and the methyl vinyl ether-maleic anhydride copolymer.

Example 8 A mixture of 141 grams (0.4 mol) of tri-caprylyl amine, 31.2 grams (0.2 mol) of the aforementioned copolymer of Example 1 and 344 grams of xylene, as a diluent, was stirred at 108 C. for a period of four hours and resulted in a xylene solution of the reaction product of the aforementioned tri-caprylyl amine and the methyl vinyl ether-maleic anhydride copolymer.

Example 9 A mixture of 200 grams (0.26 mol) of the condensation product of 1 mol of oleyldiamine and 1 mol of a mixture of tall oil fatty acids (condensed at 300 C.), 20 grams (0.13 mol) of the aforementioned copolymer of Example 1 and 220 grams of xylene, as a diluent, was stirred at 112 C. for a period of about four hours and resulted in a xylene solution of the reaction product of the aforementioned amine condensation product and the methyl vinyl ether-maleic anhydride copolymer.

In accordance with the data of the following table a series of comparative electrical conductivity tests were carried out for the purpose of determining the aforementioned properties of the compositions prepared in accordance with Examples 1 through 9 with respect to imparting anti-static properties to organic liquid compositions. The test employed for this purpose was electrical conductivity measured in picomhos (i.e. 10* mhos) per meter. In these tests the aforementioned anti-static agents were blended in a liquid hydrocarbon fuel composition comprising about 75% catalytically cracked component and about 25% straight-run component, boiling at a temperature from about 320720 F. The resulting fuel compositions were then evaluated for their degree of improvement in electrical conductivity, with the results shown in the table.

As will be seen from the data of the examples of the foregoing table, a marked improvement in anti-static properties of organic liquid compositions is obtained through the use of the anti-static additive of the present invention. It will be understood, of course, that the improved organic liquid compositions of the present invention may, if so desired, contain various other additives or mixtures of such additional additives in order to further enhance their properties. Thus, the organic liquid compositions of the present invention may also contain such additives as antioxidants, detergents, dispersants, stability improvers and the like. It will also be understood that although the present invention has been described with preferred embodiments, various modifications and adaptations thereof may be resorted to without departing from the spirit and scope of the invention, as those skilled in the art will readily understand.

We claim:

1. The solid reaction product consisting essentially of the product produced by reacting at a temperature of at least 108 C. in an inert diluent an amine with methyl vinyl ethermaleic anhydride copolymer, wherein the methyl vinyl ether and maleic anhydride are copolymerized in a mol ratio of 1:1, the amine and said copolymer are reacted in a mol ratio of from about 1:1 to about 2:1 and wherein said amine is a primary monoamine having a tertiary carbon atom attached to an amino group and containing from about 12 to about 24 carbon atoms per amine molecule.

References Cited UNITED STATES PATENTS 2,313,565 3/1943 McDowell et al. 26078 UA 2,746,837 5/1956 Kirk 26078 UA 2,985,625 5/1961 Jones 26078 UA 2,988,539 6/1961 Cohen et al 26078 UA 3,157,595 11/1964 Johnson et al 26078 UA 3,436,378 4/1969 Azorlosa et a1. 26078 UA FOREIGN PATENTS 505,120 5/1939 Great Britain 26078 UA HAROLD D. ANDERSON, Primary Examiner US. Cl. X.R.

252500; 26033.6 R, 78.4 D, 78.5 T 

